Cooling compositions including menthyl esters

ABSTRACT

This description provides cooling compositions that deliver a prolonged physiological cooling sensation to the skin or a mucous membrane. The cooling compositions may be present alone or in product such as a chewing gum or a confection. In some embodiments, the cooling compositions include menthyl glutarate and at least one additional cooling agent, which may be WS-3 or WS-23, and optionally menthol. The cooling compositions may be in a liquid form at room temperature.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.11/543,473, filed Oct. 5, 2006, which claims the benefit of U.S.Provisional Application No. 60/723,698, filed Oct. 5, 2005, the contentsof which are incorporated herein by reference.

FIELD

This description relates to cooling compositions that may be deliveredorally or to the skin or mucous membranes. The compositions contain oneor more cooling agents in combination with a menthyl ester. The coolingagent(s) and menthyl ester may be provided in one composition or theymay be provided separately in distinct formulations separated over timeor geographically.

BACKGROUND

Many substances are known to provide a sensation of cooling onapplication and are called “cooling agents.” Exemplary cooling agentsinclude menthol, isopulegol, 3-(1-menthoxy)propane-1,2-diol,3-(1-menthoxy)-2-methylpropane-1,2-diol, p-menthane-2,3-diol,p-menthane-3,8-diol,6-isopropyl-9-methyl-1,4-dioxaspiro[4,5]decane-2-methanol, menthylsuccinate and its alkaline earth metal salts, trimethylcyclohexanol,N-ethyl-2-isopropyl-5-methylcyclohexanecarboxamide, Japanese mint oil,peppermint oil, menthone, menthone glycerol ketal, menthyl lactate,3-(1-menthoxy)ethan-1-ol, 3-(1-menthoxy)propan-1-ol,3-(1-menthoxy)butan-1-ol, 1-menthylacetic acid N-ethylamide,1-menthyl-4-hydroxypentanoate, 1-menthyl-3-hydroxybutyrate,N,2,3-trimethyl-2-(1-methylethyl)-butanamide, n-ethyl-t-2-c-6nonadienamide, N,N-dimethyl menthyl succinamide, and menthyl pyrrolidonecarboxylate.

Despite the existence in the prior art and in commerce of such a vastnumber and variety of cooling agents, a need exists for a coolingcomposition that will contribute a long-lasting cooling sensation toproducts in which it is found without unwanted harshness or flavorcharacteristics. It would also be desirable to provide a clean,high-quality flavor chewing gum with a good cooling effect withoutleaving a significant aftertaste. Including mono menthyl ester-basedcompounds in food, cosmetic and fragrance applications may supply a needfor cooler compounds which provide strong and substantive refreshing andcooling attributes in the absence of negative taste, negative aroma andnegative cooling attributes. There remains a need to provide coolingcompositions which provide good onset of effect and prolonged cooling.

SUMMARY

The compounds and compositions described herein provide coolingcompositions that deliver a prolonged physiological cooling sensation tothe skin or a mucous membrane. The cooling compositions may be presentalone or in product such as a chewing gum or a confection.

In some instances, the cooling compositions may provide for delivering asensation substantially similar to that delivered by WS-3 or WS-23 aloneby administering a composition containing a menthyl ester but where theamount of WS-3 or WS-23 present in the composition can be reducedrelative to the amount of WS-3 or WS-23 alone required to provide asubstantially similar sensation.

In a first embodiment, there is provided a cooling compositionconsisting essentially of: about 5% to about 60% by weight menthylglutarate; about 5% to about 50% by weight of at least one cooling agentselected from N-ethyl-p-menthane-3-carboxamide, trimethyl isopropylbutanamide and combinations thereof; and about 15% to about 85% byweight menthol.

In some embodiments, there is provided a cooling composition consistingessentially of: about 5% to about 60% by weight of at least two menthylesters; about 5% to about 50% by weight of at least one cooling agentselected from N-ethyl-p-menthane-3-carboxamide, trimethyl isopropylbutanamide and combinations thereof; and about 15% to about 85% byweight menthol.

Some embodiments provide a cooling composition including: about 5% toabout 60% by weight menthyl glutarate; about 5% to about 50% by weightof at least one cooling agent selected fromN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof; and at least about 75% by weight of the menthylglutarate and the at least one cooling agent, wherein the composition isliquid at 25° C.

Some other embodiments provide a cooling composition including: about 5%to about 60% by weight of at least two menthyl esters; about 5% to about50% by weight of at least one cooling agent selected fromN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof, and at least about 75% by weight of the at leasttwo menthyl esters and the at least one cooling agent, wherein thecomposition is liquid at 25° C.

In some embodiments, there is a cooling composition consistingessentially of: about 5% to about 60% by weight menthyl glutarate; about5% to about 50% by weight of at least one cooling agent selected fromN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof; and about 15% to about 85% by weight menthol,wherein the composition is liquid at 25° C.

Some embodiments provide a cooling composition consisting essentiallyof: about 5% to about 60% by weight of at least two menthyl esters;about 5% to about 50% by weight of at least one cooling agent selectedfrom N-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamideand combinations thereof; and about 15% to about 85% by weight menthol,wherein the composition is liquid at 25° C.

Some other embodiments provide a cooling composition including: menthylsuccinate; a second cooling agent selected fromN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof; and a third cooling agent selected from1-isopulegol, p-menthane-3,8-diol and combinations thereof.

In some embodiments, there is provided a method of preparing a coolingcomposition which is liquid at 25° C., including the steps of:

-   (a) providing menthyl glutarate in a liquid form; and-   (b) adding at least one cooling agent selected from    N-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide and    combinations thereof to the menthyl glutarate and dissolving or    suspending the at least one cooling agent therein to form the liquid    cooling composition,-   wherein the menthyl glutarate is present in amounts of about 5% to    about 60% by weight of the composition and the at least one cooling    agent selected from N-ethyl-p-menthane-3-carboxamide, trimethyl    isopropyl butanamide and combinations thereof is present in amounts    of about 5% to about 50% by weight of the composition.

Some other embodiments provide a method of preparing a coolingcomposition which is liquid at 25° C., including the steps of:

-   (a) combining menthyl glutarate and at least one cooling agent    selected from N-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl    butanamide and combinations thereof;-   (b) heating the menthyl glutarate and the at least one cooling agent    to form a liquid composition; and-   (c) cooling the composition of the menthyl glutarate and the at    least one cooling agent to less than 30° C. while maintaining the    composition in a liquid state to form the liquid cooling    composition.

DETAILED DESCRIPTION

The description extends to products that otherwise may contain coolingcompositions such as preferably flavoring agents, foodstuffs,confections, beverages, gums, dentifrices, mouthwashes, toiletries,liniments lotions for topical application and cigarettes, such productscomprising a composition that provides a physiological sensationsubstantially the same as that provided by menthol. The coolingcompositions provide a substantially cooling physiological sensation.

Menthol is known for its physiological cooling effect on the skin andmucous membranes of the mouth and has been extensively used as aflavouring agent, being a major constituent of oil of peppermint infoodstuffs, beverages, dentifrices, mouthwashes, etc. and as a componentin a wide range of toiletries, liniments and lotions for topicalapplication. Menthol is also a well known tobacco additive for producinga “cool” sensation in the mouth when smoking. Carvomenthol has also beenreported as having a physiological cooling effect as haveN,N-dimethyl-2-ethyl butanamide and N,N-diethyl-2-ethyl butanamide asdescribed in, for instance, French Patent No. 1,572,332.

It is well established that the “cooling” effect of menthol is aphysiological effect due to the direct action of menthol on the nerveendings of the human body responsible for the detection of hot and cold.Menthol directly stimulates cold receptors. Some non-menthol compoundsproviding a physiological effect similar to menthol are described inU.S. Pat. No. 4,296,255, herein incorporated by reference.

Peppermint oil may be used to create a “cooling” in oral products suchas toothpaste, mouthwash, chewing gum, candy and other food products.Peppermint oil generally comprises about 45-55% menthol, about 20-25%menthone, about 5% menthyl acetate, about 5% eucalyptol and many otherconstituents. Peppermint oil is even used in non-peppermint products,such as spearmint or wintergreen flavored products, in order to createthis desired cooling effect. However, peppermint notes are then found inthe resulting non-peppermint flavored products.

Menthol is also known for its physiological cooling effect on the skinand mucous membranes of the mouth. Being a major constituent ofpeppermint oil, menthol has been used extensively in foods, beverages,dentifrices, mouthwashes, toiletries, lotions and the like. Thedisadvantages of using menthol, however, are its strong minty odor andthe harsh notes it imparts to compositions in which it is found. Mentholhas been used in conjunction with other cooling agents because, amongother things, it acts to prepare taste buds to receive non-mentholcooling agents. Menthol provides a light, fresh, minty sensation and insome regards prepares taste buds to receive a cooling sensation. It hasbeen reported that some cooling agents, e.g. WS-3 and WS-23, may in factdeliver an initial warming sensation if supplied without menthol.

Most confectionery products which are promoted for breath freshening aremint flavored products which contain moderate to high levels of menthol.The disadvantages of using menthol, however, are its strong minty odorand the harsh notes it imparts to compositions in which it is found. Aneed, therefore, exists for a cooling composition that will contribute along-lasting cooling sensation to products in which it is found withoutthe unwanted harshness or flavor characteristics that come from addingmenthol.

In some consumer products, especially chewing gums, it is desirable toprovide a burst of intense flavor over a slow, gentle flavor release. Inorder to provide a favorable flavor impact, some chewing gummanufacturers have added flavors to the coating of a coated chewing gum.These flavors include spearmint flavor, peppermint flavor, wintergreenflavor and fruit flavors. In addition, very strong flavors such asmenthol have often been used to provide a burst of flavor. However, atconcentrations effective to provide a burst of flavor, menthol or mintflavors also manifest a bitter, harsh, burning taste sometimes describedas a “harsh note”.

Efforts have been directed at perfecting the use of physiologicalcooling agents within chewing gum formulations to enhance flavorcomposition and control their release to enhance the flavor of chewinggum. U.S. Pat. No. 5,326,574 discloses a process for codrying thephysiological cooling agent 3-1-menthoxypropane-1,2-diol with a foodacceptable, water-soluble carrier and mixing the resulting product intochewing gum.

L-Monomenthyl glutarate has the chemical name (L)-Monomenthane-3-ylglutarate, is sometimes known as Pentadienoic acid, mono[5methyl-2-1(1-methylethyl)cyclohexyl]ester, [1L]; [1R(−)] monomenthylglutarate, and has the chemical formula C₁₅H₂₆O₄. It may be located byJECFA Number 1414, FEMA number 4006 and CAS number 220621-22-7. It ispresent as a clear viscous fluid having a minty, menthol-like aroma.

Cooling Agents

The term “physiological cooling agent” encompasses any number ofphysiological cooling agents. However, in the context of thisdescription, the term “physiological cooling agent” does not includetraditional flavor-derivatives such as menthol or menthone. Preferredphysiological cooling agents do not have a perceptible flavor of theirown, but simply provide a cooling effect.

An optional additional component of the cooling compositions is aphysiological cooling agent. Suitable levels of the cooling agent arefrom about 0.001 to about 85%, preferably from about 0.01 to about 50%,more preferably from about 0.05 to about 15% by weight of the coolingcomposition, and still more preferably from about 0.10 to about 5% byweight of the composition.

Generally, the compositions will contain an amount of the active coolingcompounds sufficient to stimulate the cold receptors in the areas of theskin or mucous membrane with which the compositions come into contactand thereby promote the desired cold sensation. As the degree andlongevity of cooling sensation varies from compound to compound thequantity of stimulant used in each composition will vary widely. As aguide, it may be said that, with the more active compounds, asignificant cooling sensation, which, in some cases, may persist forseveral hours, can be achieved upon application to the mucosa or skin ofas little as 0.05 ml. of a 1.0% weight percent solution of the activeingredient in ethanol. For the less active compounds a significantcooling effect can be achieved only with more concentrated solutions,e.g. 5.0% by weight or more of the active ingredient. It must also beadmitted that such skin tests are somewhat subjective, some individualsexperiencing a greater or lesser cooling sensation than others whensubjected to the same test.

Cooling agents are well known in the art and are described in, forinstance, U.S. Pat. Nos. 4,032,661, 4,070,449, 4,033,994, 4,296,093,4,296,255, 4,230,688, 4,034,109, 4,020,153, 4,136,163, 5,266,592, U.S.Publication Nos. 2004/0067970 and 2005/0019455, and by Leffingwell etal., “Cool without Menthol & Cooler than Menthol and Cooling Compoundsas Insect Repellents,” the disclosures of which are herein incorporatedby reference. A test for physiological cooling agents is described inGB-A-1,452,291, published Oct. 13, 1976, reproduced in part herein belowfor convenience. Cooling agents are well known in the art. Preferredphysiological cooling agents do not have a perceptible flavor of theirown, but simply provide a cooling effect. Since the physiologicalcooling agents do not have their own perceptible flavor, they can beused with other types of flavors to offer new and unique advantages,such as breath freshening. Several U.S. and foreign references disclosespecific compounds and classes of compounds that are physiologicalcooling agents that may be used in the present compositions. Some ofthese disclose the use of physiological cooling agents in chewing gum.These include, for instance, U.S. Pat. No. 5,451,404 (a ketal combinedwith another coolant (menthol or carboxamides)); U.S. Pat. No. 5,372,824(physiological cooling agents and reduced menthol); U.S. Pat. No5,348,750 (menthone ketals); U.S. Pat. No. 5,326,574 (a spray dried3-1-menthoxypropane-1,2-diol-); U.S. Pat. No. 5,266,592 (menthoneglycerol ketals); U.S. Pat. No. 5,165,943 (a cyclodextrin complex withphysiological cooling agents); U.S. Pat. No. 5,009,893 (p-menthanecarboxamide physiological cooling agent with menthol for reducedbitterness); U.S. Pat. No. 4,459,425 (3-1-menthoxypropane-1,2-diol);U.S. Pat. No. 4,296,093 (substituted cyclohexanamides); U.S. Pat. Nos.4,248,859 and 4,318,900 (alkyl substituted alicyclic carboxylic acids,esters or amides); U.S. Pat. Nos. 4,157,384 and 4,029,759 (various3-substituted p-menthanes); U.S. Pat. No. 4,081,480(alpha-oxy(oxo)mercaptan alkanes); U.S. Pat. No. 4,070,449 (sulphoxidesand sulphones); U.S. Pat. Nos. 4,060,091; 4,190,643 and 4,136,163(substituted p-menthane-3-carboxamides); U.S. Pat. Nos. 4,153,679;4,296,255 and 4,230,688 (acyclic carboxamides); U.S. Pat. No. 4,034,109(acyclic sulphonamides and sulphinamides); U.S. Pat. No. 4,033,994(p-menthane-3-carboxylates); U.S. Pat. Nos. 3,793,446 and 3,644,613(ketoesters of menthol); U.S. Pat. No. 3,720,762 (spilanthol withmenthol or peppermint oil); Canadian Patent No. 2,101,790 (carbonicacids having free polar groups); German Patent No. 2,608,226 (menthyllactate); German Patent No. 2,433,165 (N-acetylglycine menthyl ester);French Patent No. 2,577,922 (L-menthyl-3-hydroxybutyrate); JapanesePatent No. 94/065023 (2-isopropenyl-5-methylcyclohexanol); Great BritainPatent No. 1,502,680 (bicyclic acids, esters, amides and substitutedmenthanols); Great Britain Patent No. 1,476,351 (cyclic and acyclicamides, ureas and sulphonarnides); Great Britain Patent No. 1,442,998(trialkyl-substituted cyclohexane carboxamides); Great Britain PatentsNos. 1,421,744 and 1,421,743 (novel amides); Great Britain Patent No.1,411,786 (cyclohexanamides); Great Britain Patent No. 1,404,596(acyclic secondary and tertiary alkanols); PCT Publication No. WO97/07771 (menthyl succinate and carboxamides); PCT Publication No. WO96/28133 (coolant composition for comestibles); PCT Publication No. WO96/17524 (a cooling composition comprising N-substituted p-menthanecarboxamides and menthol); PCT Publication No. WO 94/010117(cyclohexanol derivatives); and U.S. S. Pat. No. 3,639,569(physiological cooling agents). U.S. Pat. Nos. 4,032,661, 4,070,449,4,033,994, 4,296,093, 4,296,093, 4,296,255, 4,230,688, 4,034,109,4,020,153, 5,009,893, 5,698,181, 5,266,592, U.S. Publication Nos.2004/0067970 and 2005/0019455, and Leffingwell et al., “Cool withoutMenthol & Cooler than Menthol and Cooling Compounds as InsectRepellents,” the disclosures of which are also herein incorporated byreference provide yet further examples. A test for physiological coolingagents is described in GB-A-1,452,291, published Oct. 13, 1976,reproduced in part herein below for convenience.

Among the useful cooling agents are included xylitol, erythritol,dextrose, sorbitol, menthane, menthone, ketals, menthone ketals,menthone glycerol ketals, substituted p-menthanes, acyclic carboxamides,mono menthyl glutarate, substituted cyclohexanamides, substitutedcyclohexane carboxamides, substituted ureas and sulfonamides,substituted menthanols, hydroxymethyl and hydroxymethyl derivatives ofp-menthane, 2-mercapto-cyclo-decanone, hydroxycarboxylic acids with 2-6carbon atoms, cyclohexanamides, menthyl acetate, menthyl salicylate,N,2,3-trimethyl-2-isopropyl butanamide (WS-23),N-ethyl-p-menthane-3-carboxamide (WS-3), ethyl ester ofN-[[5-methyl-2-(1-methylethyl)cyclohexyl]carbonyl]glycine (WS5), as wellas the substantially pure ethyl ester ofN-[[5-methyl-2-(1-methylethyl)cyclohexyl]carbonyl]glycine as disclosedin U.S. Pat. No. 7,189760 to Erman, et al which is incorporated in itsentirety herein by reference, isopulegol, menthyloxy propane diol,3-(1-menthoxy)propane-1,2-diol, 3-(1-menthoxy)-2-methylpropane-1,2-diol,p-menthane-2,3-diol, p-menthane-3,8-diol,6-isopropyl-9-methyl-1,4-dioxaspiro[4,5]decane-2-methanol, menthylsuccinate and its alkaline earth metal salts, trimethylcyclohexanol,N-ethyl-2-isopropyl-5-methylcyclohexanecarboxamide, Japanese mint oil,peppermint oil, 3-(1-menthoxy)ethan-1-ol, 3-(1-menthoxy)propan-1-ol,3-(1-menthoxy)butan -1-ol, 1-menthylacetic acid N-ethylamide,1-menthyl-4-hydroxypentanoate, 1-menthyl-3-hydroxybutyrate,N,2,3-trimethyl-2-(1-methylethyl)-butanamide, n-ethyl-t-2-c-6nonadienamide, N,N-dimethyl menthyl succinamide, substitutedp-menthanes, substituted p-menthane-carboxamides,2-isopropanyl-5-methylcyclohexanol (from Hisamitsu Pharmaceuticals,hereinafter “isopregol”); menthone glycerol ketals (FEMA 3807, tradenameFRESCOLAT® type MGA); 3-1-menthoxypropane-1,2-diol (from Takasago, FEMA3784); and menthyl lactate; (from Haarman & Reimer, FEMA 3748, tradenameFRESCOLAT® type ML), WS-30, WS-14, Eucalyptus extract(p-Mehtha-3,8-Diol), Menthol (its natural or synthetic derivatives),Menthol PG carbonate, Menthol EG carbonate, Menthol glyceryl ether,N-tertbutyl-p-menthane-3-carboxamide, P-menthane-3-carboxylic acidglycerol ester, Methyl-2-isopryl-bicyclo (2.2.1), Heptane-2-carboxamide;Menthol methyl ether, menthyl pyrrolidone carboxylate, cyclic α-ketoenamines, cyclotene derivatives such as cyclopentenes including3-methyl-2-(1-pyrrolidinyl)-2-cyclopenten-1-one and5-methyl-2-(1-pyrrolidinyl)-2-cyclopenten-1-one, compounds of theformula:

wherein B is selected from H, CH3, C2H5, OCH3, 0C2H5; and OH; andwherein A is a moiety of the formula-CO-D, wherein D is selected fromthe following moieties: (i)-NR1R2, wherein R′ and R2 are independentlyselected from H and C 1-C8 straight or branched-chain aliphatic,alkoxyalkyl, hydroxyalkyl, araliphatic and cycloalkyl groups, or R1 andR2 together with the nitrogen atom to which they are attached form partof an optionally-substituted, five-or six-membered heterocyclic ring;(ii)-NIICH2COOCH2CH3, —NHCH2CONH2, —NHCH2CH2OCH3, —NHCH2CH2OH,—NHCH2CH(OH)CH2OH and (iii) a moiety selected from the group consistingof:

as disclosed in PCT Patent Application WO2006/125334 to Bell et al whichis incorporated in its entirety herein by reference, among others. Theseand other suitable cooling agents are further described in the followingU.S. patents, all of which are incorporated in their entirety byreference hereto: U.S. Pat. No. 4,230,688; 4,032,661; 4,459,425;4,178,459; 4,296,255; 4,136,163; 5,009,893; 5,266,592; 5,698,181;6,277,385; 6,627,233; 7,030,273. Still other suitable cooling agents arefurther described in the following U.S. Patent Applications, all ofwhich are incorporated in their entirety by reference hereto: U.S.2005/0222256; 2005/0265930.

Particular examples of physiological cooling agents include, forinstance, substituted p-menthanes, substituted p-menthane-carboxamides(e.g., N-ethyl-p-menthane-3-carboxamide (FEMA 3455)), acycliccarboxamides, substituted cyclohexanamides, substituted cyclohexanecarboxamides, substituted ureas and sulphonamides, and substitutedmenthanols (all from Wilkinson Sword); hydroxymethyl and hydroxyethylderivatives of p-menthane (from Lever Bros.); menthyl succinate;2-mercapto-cyclo-decanone (from International Flavors and Fragrances);2-isopropanyl-5-methylcyclohexanol (from Hisamitsu Pharmaceuticals,hereinafter “isopregol”); hydroxycarboxylic acids with 2-6 carbon atoms;menthone glycerol ketals (FEMA 3807, trade name FRESCOLAT® type MGA);3-1-menthoxypropane-1,2-diol (from Takasago, FEMA 3784, (hereinafter“TCA”)); and menthyl lactate; (from Haarman & Reimer, FEMA 3748, tradename FRESCOLAT® type ML).

While any of the above-disclosed physiological cooling agents may beused in chewing gum and confectioneries, some preferred physiologicalcooling agents are substituted p-menthane carboxamides (PMC), such asthose disclosed in U.S. Pat. Nos. 4,060,091; 4,190,643 and 4,136,163,all assigned to Wilkinson Sword, especiallyN-ethyl-p-menthane-3-carboxamide (called WS-3); acyclic carboxamides(AC), such as those disclosed in U.S. Pat. Nos. 4,296,255; 4,230,688;and 4,153,679; all assigned to Wilkinson Sword, especiallyN-2,3-trimethyl-2-isopropyl butanamide (called WS-23); menthone glycerolketal (MGK); menthyl lactate (ML); menthyl succinate (MS); and3-1-menthoxypropane-1,2-diol (TCA).

Other preferred physiological cooling agents are described inW097/06695. Some include menthol, peppermint oil,N-substituted-p-menthane-3-carboxamides, acyclic tertiary and secondarycarboxamides, 3-1-menthoxy propan-1,2-diol and mixtures thereof. Somecarboxamides found most useful are those described in U.S. Pat. No.4,136,163, Jan. 23, 1979 to Watson et al., and U.S. Pat. No. 4,230,688,Oct. 28, 1980 to Rowsell et al. The carboxamides in U.S. Pat. No.4,136,163 are N-substituted-p-menthane-3-carboxamides.N-ethyl-p-menthane-3-carboxamide, commercially available as WS-3 fromWilkinson Sword, is preferred herein. The carboxamides of U.S. Pat. No.4,230,688 are certain acyclic tertiary and secondary carboxamides, ofwhich trimethyl isopropyl butanamide, commercially available as WS-23from Wilkinson Sword is one preferred cooling agent for use herein.Other preferred acyclic carboxamides include acyclic tertiary andsecondary carboxamides including the compounds commercially known as Ice6000, 10000, and 11000. Other cooling compounds include WS-3, WS-14,WS-23, WS-5 and the like.

The following test procedure can be used as a means to identifycompounds having a physiological cooling activity. This test is intendedpurely as a means for identifying compounds having a physiologicalcooling agent activity and useful in the present compositions and forgiving an indication of the different relative activities of thecompounds, as between themselves and as compared with menthol, whenapplied in particular manner to a particular part of the body. Theresults are not necessarily indicative of the activity of thesecompounds in other formulations and other parts of the body where otherfactors come into play. For example, a controlling factor in the onsetof cooling effect, its intensity and longevity will be the rate ofpenetration of the compounds through the epidermis or mucous membraneand this will vary in different locations on the human body. Theformulation of actual products will therefore be done largely on anempirical basis although the test results and other figures given hereinwill be useful as a guide, particularly in the formulation of productsfor oral administration, since the test procedure to be describedinvolves oral application of the compound. A similar test may, ofcourse, be devised for the purposes of measuring the relative activitiesof the compounds of another area of the body, for example, the face orforearm, and this will be a useful guide in the choice of compounds tobe used in preparations for external topical usage. It will also benoted that the described test procedure can be done on a statisticalbasis. This is necessary since sensitivity to these compounds will varynot only from compound to compound and from one part of the body toanother, but also from one individual to another. Tests of this natureare commonly used in the testing of the organoleptic properties e.g.taste and smell of organic and inorganic compounds, see Kirk-Othmer:Encyclopedia of Chemical Technology, 2nd Ed. (1967) Vol. 14, pages336-344.

The following test procedure is aimed at determining the minimumquantity of the test compound required to produce a noticeable coolingeffect in a person of average sensitivity, this minimum quantity beingtermed the threshold for that particular compound. The tests are carriedout on a selected panel of 6 people of median sensitivity to 1-menthol.

In some embodiments, the following procedure may be used to select apanel. Known quantities of 1-menthol in solution in petroleum ether (bp.40-60° C.) are placed on 5 mm squares of filter paper, after which thesolvent can be allowed to evaporate. A panel of observers can beenrolled and asked to place one impregnated square at a time on thetongue and to report on the presence or absence of a cooling effect. Thequantity of 1-menthol on each impregnated square is gradually reducedfrom a value substantially above 0.25 micrograms per square tosubstantially below 0.25 micrograms, the precise range being immaterial.Conveniently, one starts with squares containing 2.0 micrograms beinghalf that of the preceding square, i.e. the second test square willcontain 1.0 microgram, the third 0.5 microgram, and so on. Each quantitycan be tested on the tongue at least ten times. In this way, thethresholds to cold receptor stimulus by 1-menthol are determined foreach individual of the panel, the threshold for each individual beingthat amount of 1-menthol for which, in a series of not less than tentest applications, a cooling effect is reported 50% of the time. Sixpanel members can be selected whose threshold to 1-menthol is in therange 0.1 micrograms to 10 micrograms and whose average threshold isapproximately 0.25 micrograms, this select panel being regarded as thetest panel of average sensitivity.

To test the activity of cooling agents, the above procedure can berepeated using only the six selected panel members of averagesensitivity to 1-menthol. The individual thresholds for each testcompound on each of the six selected panel members are determined andaveraged. Those compounds whose average threshold on the select testpanel is 100 micrograms or less, preferably 50 micrograms or less areregarded as having cooling activity.

The balance of the cooling composition can be made up of a suitableappropriate carrier, such as water or a bulk sweetener, described inmore detail below.

Menthyl Esters

U.S. Pat. No. 3,111,127 incorporated herein by reference discloses suchmonomenthyl esters as monomenthyl succinate, monomenthyl αα-dimethylsuccinate and monomenthyl 2-methylmaleate. U.S. Pat. No. 4,150,052incorporated herein by reference discloses the use of N-ethylp-menthane-3-carboxamide for its physiological cooling action on theskin, and discloses its use in, for example, chewing gum. U.S. Pat. Nos.5,725,865 and 5,843,466 incorporated herein by reference disclose theuse of mono menthyl succinate for its physiological cooling action anddisclose its use in, for example, carbonated beverages, alcoholicbeverages and chewing gum. U.S. Pat. No. 6,365,215 incorporated hereinby reference discloses the use of mono menthyl glutarate in oral sensoryperception-affecting compositions for use with such consumable materialsas chewing gums. U.S. Pat. No. 6,451,844 incorporated herein byreference discloses the use of menthyl 2-pyrrolidone-5-carboxylate(QUESTICE L, Quest International, B.V. of Naarden, Netherlands) in skincare and hair care compositions for their insect repellency properties.

Furthermore, L-mono menthyl glutarate has been registered as a GRASflavoring substance, FEMA No. 4006 and, in Smith et al., “GRAS FlavoringSubstances 20”, Food Technology, Vol. 55, No. 12, December 2001 at page53 is indicated to have uses in nonalcoholic beverages, alcoholicbeverages, chewing gum, confectionery frosting, hard candy, soft candyand snack foods.

A number of the mono menthyl half acid ester derivatives are found to beuseful such as (i) L-menthyl hydrogen adipate (n=3); (ii) L-menthylhydrogen pimelate (n=4); and (iii) L-menthyl hydrogen suberate (n=5) asdisclosed by Rule et al., “Optical Activity and the Polarity ofSubstituent Groups Part VIII. Growing-chain Effects and the ortho-Effectin Benzoic Esters”, J. Chem. Soc. 1928 (Part 1), pp. 1347-1361.

In addition, a lower adjacent methylene homologue of the genus of novelcompounds is disclosed in “SciFinder” (Nov. 20, 2002; Trademark ofChemical Abstracts Services), to with: malonamic acid, p-menth-3-ylester, (.+−.)-(8CI) having CAS Registry Number 6129-88-0.

Definitions

By “cooling agent” is meant any agent whether described herein, known inthe art as producing, or otherwise capable of producing a sensationdescribed as cooling by those experiencing it on the skin, oral cavityor mucous membranes.

By “aroma” is meant a minty or freshening physiological sensationperceived as a sense of smell.

By “cooling effect” is meant a sensation described as cooling by thoseexperiencing it on the skin, oral cavity or mucous membranes.

By phrases such as “the amount of WS-23 present in the composition,chewing gum or confection is reduced relative to the amount of WS-23alone required to provide the substantially similar sensation” or “theamount of WS-3 present in the composition, chewing gum or confection isreduced relative to the amount of WS-3 alone required to provide thesubstantially similar sensation” is meant that on average, respondentsevaluating the “cooling” sensation provided by the cooling compositionquantify the “cooling” sensation as substantially equivalent to thatprovided by WS-23 or WS-3 alone even though WS-23 or WS-3 are present inamounts that are at least 5%, at least 10%, at least 20%, at least 30%or at least 40% or even 50% less by mass.

By “Menthyl ester” is meant a class of compounds such as those describedin, for instance, U.S. Pat. No. 3,111,127, U.S. Pat. No. 6,365,215 andU.S. Pat. No. 6,884,906 the disclosures of which are herein incorporatedby reference, including monomenthyl succinate, dimenthyl succinate,monomenthyl α,α-dimethyl succinate and monomenthyl2-methylmaleatementhyl glutarate, FEMA 4006, as described, supra. Also,are intended derivatives thereof, such as for example, the menthyl halfacid ester derivatives set forth in U.S. Pat. No. 6,884,906. The term isalso intended to embrace the alkali metal salts and alkaline earth metalsalts of the menthyl compounds such as monomenthyl succinate andmonomenthyl glutarate. Menthyl esters also include menthyl acetate,1-menthyl acetate, d,1-menthyl acetate, homomenthyl acetate, menthyllactate, and 1-menthyl lactate.

Cooling Compositions

Some embodiments provide cooling compositions including about 5% toabout 60% by weight menthyl glutarate, about 5% to about 50% by weightof at least one cooling agent selected fromN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof, and about 15% to about 85% by weight menthol. Thecooling composition may consist essentially of these components in someembodiments.

In some embodiments, the cooling compositions include about 5% to about60% by weight of at least two menthyl esters, about 5% to about 50% byweight of at least one cooling agent selected fromN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof, and about 15% to about 85% by weight menthol. Thecooling composition may consist essentially of these components in someembodiments.

Some other embodiments provide cooling compositions including menthylsuccinate, a second cooling agent selected fromN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof, and a third cooling agent selected from1-isopulegol, p-menthane-3,8-diol and combinations thereof. The coolingcomposition may consist essentially of these components in someembodiments. The menthyl succinate may be present in amounts of about 5%to about 60% by weight of the composition. The second cooling agent maybe present in amounts of about 5% to about 50% by weight of thecomposition. The third cooling agent may be present in amounts of about2% to about 50% by weight of the composition.

In some embodiments, the cooling composition may be a liquid at roomtemperature (about 25° C.). For instance, a cooling composition, whichis liquid at 25° C., may include about 5% to about 60% by weight menthylglutarate and about 5% to about 50% by weight of at least one coolingagent selected from N-ethyl-p-menthane-3-carboxamide, trimethylisopropyl butanamide and combinations thereof. The combination of thementhyl glutarate and the at least one cooling agent may be present inamounts of at least about 75% by weight of the cooling composition.Menthol also may be included in some embodiments, for instance, about15% to about 85% by weight.

In some embodiments, cooling compositions that are liquid at 25° C. mayinclude about 5% to about 60% by weight of at least two menthyl estersand about 5% to about 50% by weight of at least one cooling agentselected from N-ethyl-p-menthane-3-carboxamide, trimethyl isopropylbutanamide and combinations thereof. The combination of the at least twomenthyl esters and the at least one cooling agent may be present inamounts of at least about 75% by weight of the cooling composition,Menthol also may be included in some embodiments, for instance, about15% to about 85% by weight.

In some embodiments, the cooling composition, which is liquid at 25° C.,may consist essentially of about 5% to about 60% by weight menthylglutarate, about 5% to about 50% by weight of at least one cooling agentselected from N-ethyl-p-menthane-3-carboxamide, trimethyl isopropylbutanamide and combinations thereof, and about 15% to about 85% byweight menthol.

In some other embodiments, the cooling composition, which is liquid at25° C., may consist essentially of about 5% to about 60% by weight of atleast two menthyl esters, about 5% to about 50% by weight of at leastone cooling agent selected from N-ethyl-p-menthane-3-carboxamide,trimethyl isopropyl butanamide and combinations thereof, and about 15%to about 85% by weight menthol.

The liquid cooling compositions may be prepared by first providingmenthyl glutarate, or at least two menthyl esters in some embodiments,in liquid form. Because menthyl glutarate has a low melting point, it isa liquid at room temperature (about 25° C.). At least one cooling agentselected from N-ethyl-p-menthane-3-carboxamide, trimethyl isopropylbutanamide and combinations thereof may be added to the liquid menthylglutarate. N-ethyl-p-menthane-3-carboxamide and trimethyl isopropylbutanamide are both solids at room temperature. Solid cooling agents aretypically dissolved in a solvent prior to incorporation into chewinggums and confectioneries to improve the ability to mix them into suchproducts. Because menthyl glutarate is a liquid, the solid coolingagents may be dissolved or suspended directly in the liquid menthylglutarate to form the liquid cooling composition. This may be done atroom temperature in the absence of added heat. This composition can beformed as a premix at room temperature. Accordingly, an additionalsolvent is not needed to dissolve the solid cooling agents.

In some embodiments, it may be desirable to heat the combination ofcooling agents to melt the cooling agents that are solids at roomtemperature. In particular, although menthyl glutarate is a liquid, manycooling agents are solids at room temperature. After being melted, suchcooling agents will solidify and recrystallize upon cooling. Suchrecrystallization can make it difficult to add these cooling agents intochewing gums and confectioneries. For instance, the following coolingagents have melting points near or above room temperature: menthol (43°C.); WS-3 (88° C.); WS-23 (62-64° C.); menthyl lactate (40-42° C.);menthyl succinate (59-61° C.); and menthyl acetate ester (23-24° C.).Once such additional cooling agents are added to the menthyl glutarate,or at least two menthyl esters, therefore, it may be desirable to heatthe composition to melt the cooling agents that are solids. Forinstance, in some embodiments, the composition may be heated to meltWS-3, WS-23 and/or menthol. The composition may be heated to atemperature of at least about 65° C. The liquid composition then may becooled to less than about 30° C., more specifically about 25° C., whilemaintaining the composition in a liquid state. This provides a liquidcooling composition that is stable for a period of time at roomtemperature without recrystallization of the cooling agents that aretypically solids at room temperature. For instance, the liquid coolingcomposition desirably is stable at room temperature for a period of atleast about one hour.

The cooling compositions can be used in any products intended for oral,skin or mucosal delivery as a component for providing sensation ofcooling and for providing a physiological effect that is substantiallycooling. The products for which the compositions are useful include, butare not limited to, food and drink, such as candies, drops, chewinggums, tablets, chocolates, cakes, cookies, snack food, bread, tea,coffee, juice, fruit drinks, fruit wine, dairy drinks, carbonatedbeverages, alcoholic beverages and seasonings; and oral carepreparations, such as mouthwash, toothpaste, nebulizers, drinks,medicinal drops, gargles, and chewables.

The following illustrate a more comprehensive range of products intowhich the active cooling composition can be incorporated. These include,for instance, edible or potable compositions including alcoholic andnon-alcoholic beverages, confectionery, chewing gum; cachous; ice cream;jellies. These further include toiletries including after shave lotions,shaving soaps, creams and foams, toilet water, deodorants andantiperspirants, “solid colognes,” toilet soaps, bath oils and salts,shampoos, hair oils, talcum powders, face creams, hand creams, sunburnlotions, cleansing tissues, dentifrices, toothpicks, mouthwashes, hairtonics, eye drops. Additionally, the range extends to medicamentsincluding antiseptic ointments, pile ointments, liniments, lotions,decongestants, counter-irritants, cough mixtures, throat lozenges,antacid and indigestion preparations, oral analgesics. Also contemplatedare tobacco preparations including cigars, cigarettes, pipe tobacco,chewing tobacco and snuff; tobacco filters, especially filter tips forcigarettes. Even further are contemplated miscellaneous compositionssuch as water soluble adhesive compositions for envelopes, postagestamps, adhesive labels etc.

The edible and potable compositions will contain the active coolingcomposition in combination with an edible carrier and usually aflavoring or coloring agent. In general, the cooling composition may bepresent in amounts in the range 0.0005 to 5% by weight based on thetotal composition. Similar considerations apply to the formulation ofbeverages. In general, the amount of the cooling composition used willgenerally be in the range 0.0005 to 2.5% by weight based on the totalcomposition. Because of the cooling sensation imparted to the skin, theamount of the cooling composition added to toiletries will usually be inthe range 0.1 to 10% by weight based on the total composition.Medicaments will normally feature an amount of the cooling compositionof from 0.01 to 2.0% by weight. Tobacco preparations may contain aslittle as 0.1 mg. of the composition.

In addition to the cooling composition described herein, these productscan contain other additives according to use. For example, additivespermitted by Food Sanitation Law can be added to food and drinkaccording to necessity. Useful additives include saccharides,sweeteners, inorganic salts, emulsifiers, acidifiers, flavorings,colors, antioxidants, raising agents, thickeners, vegetable oils, milk,and other dairy products. In some detail, bakery products can comprisewheat flour (base), butter, a raising agent, e.g., baking powder, anemulsifier, e.g., a sucrose fatty acid ester, saccharides, e.g., sugar,inorganic salts, and flavorings. Chocolate can comprise cacao mass(base) cacao butter, saccharides, e.g., sugar, milk, and an emulsifier.Emulsified dressings can comprise salad oil, water, vinegar, sugar,thickening polysaccharides, and sweeteners. Chewing gum can comprise agum base, saccharides, such as sugar, glucose and starch syrup, andflavors. Candy can comprise saccharides, acidifiers, e.g., citric acid,sweeteners, flavorings, and colors. Orange fruit drinks can compriseorange juice, sweeteners, e.g., isomerized sugars, acidifiers, e.g.,citric acid, and antioxidants, e.g., vitamin C. Fruit milk drinks cancomprise fruit juice, dairy products such as milk and powdered skimmilk, saccharides, e.g., sugar, stabilizers, e.g., carboxymethylcellulose, acidifiers, e.g., citric acid, and flavorings, e.g., apineapple flavor.

In particular embodiments, the cooling compositions are used in chewinggums. Some chewing gum formulations are described in, for instance, U.S.Pat. No. 6,627,233, 6,685,916 and 6,696,044, herein incorporated byreference. Additives which can be used in the preparations includeinorganic salts, inorganic oxides, organic salts, thickeners, wettingagents, emulsifiers, surface active agents, humectants, alcohols, coloradditives, flavorings, and, if desired, medical ingredients such ascrude drugs, hemostatics, circulation stimulants, anti-inflammatoryagents, astringents, antibacterial and/or antifungal agents, andbactericides. In particular embodiments, toothpaste can compriseabrasives, such calcium phosphate, as calcium carbonate, aluminumhydroxide, silica, and calcium pyrophosphate; wetting agents, such asglycerin, sorbitol, and propylene glycol; tackifiers, such ascarboxymethyl cellulose, carrageenan, and hydroxyethyl cellulose;surface active agents, such as sodium laurylsulfate, N-acylglutaminates,and sucrose fatty acid esters; sweeteners, such as saccharin sodium,stevioside, and xylitol; and medicinal components, such as vitamin E,azulene, aluminum chlorohydroxy allanthoinate, dextranase, hinokitiol,lysozyme chloride, and chlorhexidine.

Chewing Gum Compositions

In particular embodiments, the cooling compositions are used in chewinggums and confectioneries. Compositions of chewing gum andconfectionaries are well known in the art and described in depth in, forinstance, U.S. Pat. Nos. 6,685,916, 6,627,233, 6,685,916 and 6,696,044,the disclosures of which are incorporated by reference and some of whichis summarized herein.

Chewing gum compositions typically include one or more of gum bases,flavoring agent and bulk sweeteners. The term “confectioneries” as usedherein includes, but is not limited to: nougats, candies, panning goods,gel confections, fondants, lozenges, hard boiled candies, mints,troches, pastilles, microcapsules, and fast-dissolving solid formsincluding freeze dried forms (cakes, wafers, thin films, and tablets)and fast dissolving solid forms including compressed tablets. The term“fast dissolving solid form” as used herein means that the solid dosageform dissolves in less than about 60 seconds, preferably less than about15 seconds, more preferably less than about 5 seconds, in the oralcavity. Lozenges include discoid shaped solids comprising a therapeuticagent in a flavored base. The base may be a hard sugar candy,glycerinated gelatin, or a combination of sugar with sufficient mucilageto give it form. Lozenge compositions (compressed tablet type) typicallyinclude one or more fillers (compressible sugar), flavoring agents andlubricants.

The chewing gum compositions may be coated or uncoated and be in theform of slabs, sticks, pellets, balls, compressed tablets, and the like.The composition of the different forms of the chewing gum compositionswill be similar but may vary with regard to the ratio of theingredients. For example, coated gum compositions may contain a lowerpercentage of softeners. Pellets and balls have a small chewing gumcore, which can then be coated with either a sugar solution or asugarless solution to create a hard shell. Slabs and sticks are usuallyformulated to be softer in texture than the chewing gum core. In orderto overcome any detrimental softening effect the surfactant active mayhave on the gum base, it is preferred to formulate a slab or stick gumhaving a firmer texture (i.e. with less softener than is typicallyemployed). Compressed tablets are formed from compressible mixtures.

The cooling compositions may be used in either regular chewing gum,pressed gum or bubble gum, a subset of “chewing gums.” Center filled gumis another common chewing gum form. The gum portion has a similarcomposition and mode of manufacture to that described above. However,the center fill is typically an aqueous solution or gel, which can beinjected into the center of the gum during processing. The coolingagents and compositions could optionally be incorporated together orsingly into the center fill during manufacture of the fill or into thechewing gum. The center fill gum may also be optionally coated and maybe prepared in various forms such as in the form of a lollipop.

It is preferred to use a coated gum wherein the cooling compositionsdescribed herein are in at least one of the core and the coating.

The chewing gum composition includes gum base and most of the othertypical chewing gum composition components such as sweeteners,softeners, flavoring agents and the like. The chewing gum compositionmay contain a reduced amount of softening agents such as lecithin orglycerin or may eliminate softeners. In addition, the chewing gumcomposition may contain a larger or smaller amount of sugar alcoholsthan conventional chewing gum compositions to facilitate delivery.

In accordance with one aspect of the chewing gum composition, thecooling compositions are added during the manufacture of the chewing gumcomposition, that is, with the sweeteners, flavoring agents and thelike.

In a further aspect, the gum base generally comprises elastomers,elastomer plasticizers, waxes, fats, oils, emulsifiers, fillers,texturizers and may include a desirable combination of the heating andcooling agents or warming composition. Elastomers constitute from about5% to 95% by weight of the base, preferably 10% to 70% by weight andmost preferably 15% to 45% by weight. Examples of elastomers includesynthetic elastomers such as polyisobutylene, polybutylene,isobutylene-isoprene co-polymers, styrene-butadiene co-polymers,polyvinylacetate and the like. Elastomers may also include naturalelastomers such as natural rubber as well as natural gums such asjelutong, lechi caspi, perillo, massaranduba balata, chicle, gutta hangkang or mixtures thereof. Other elastomers are known to those ofordinary skill in the art.

Elastomer plasticizers modify the firmness of the finished gum when usedin the gum base. Elastomer plasticizers are typically present in anamount of up to about 75% by weight of the gum base, preferably fromabout 5% to 45% by weight and more preferably from about 10% to 30% byweight. Examples of elastomer plasticizers include natural rosin esterssuch as glycerol ester of partially hydrogenated rosin, glycerol esterof tall oil rosin, pentaerythritol esters of partially hydrogenatedrosin, methyl and partially hydrogenated methyl esters of rosin, and thelike. Synthetic elastomer plasticizers such as terpene resins may alsobe employed in gum base composition.

Waxes include synthetic and naturally occurring waxes such aspolyethylene, bees wax, carnauba and the like. Petroleum waxes suchparaffin may also be used. The waxes may be present in the amount of upto about 30% by weight of the gum base. Waxes aid in the curing of thefinished gum and help improve the release of flavor and may extend theshelf life of the product.

Fillers modify the texture of the gum base and aid processing. Examplesof such fillers include magnesium and aluminum silicates, clay, alumina,talc, titanium oxide, cellulose polymers, and the like. Fillers aretypically present in an amount of from 1% to 60% by weight.

Examples of softeners used in the gum base include hydrogenated andpartially hydrogenated vegetable oils, cocoa butter, glycerolmonostearate, glycerol triacetate, di- and triglycerides, fatty acidssuch as stearic acid, palmitic acid, oleic acid, linoleic acid,linolenic acid and the like.

The gum base constitutes between 5% and 95% by weight of the chewing gumcomposition, more typically 10% to 50% by weight, and most typicallyfrom about 25% to 35% by weight of the chewing gum. A higher amount ofgum base is preferred.

Other ingredients used in chewing gum compositions include sweeteners,both natural and artificial and both sugar and sugarless. Sweeteners aretypically present in the chewing gum compositions in amounts of fromabout 20% to 80% by weight, preferably from about 30% to 60% by weight.Sugarless sweeteners include, but are not limited sugar alcohols such assorbitol, mannitol, xylitol, hydrogenated starch hydrolysates, maltitoland the like may also be present. High intensity sweeteners such assucralose, aspartame, neotame, salts of acesulfame, and the like aretypically present up to about 1.0% by weight.

Flavoring agents, which can vary over a wide range, may be selected inamounts from about 0. 1% to 10.0% by weight, preferably from about 0.5%to 5.0% by weight. Flavoring agents for use in chewing gum compositionsare well known and include citrus oils, peppermint oil, spearmint oil,oil of wintergreen, menthol, cinnamon, ginger and the like.

Softeners may be present to modify the texture of the chewing gumcomposition. As in typical gum compositions, softeners in thecompositions are typically present in amounts of from about 0.5% to 10%by weight based on the total weight of the chewing gum composition.

Other materials, which may be present in the gum composition includeantioxidants (e.g. butylated hydroxyanisole, butylated hydroxytoluene,beta-carotenes, tocopherols), colorants, flavoring agents and the like.

Coating techniques for applying a coating for a chewing gum compositionsuch as pan and spray coating are well known. Preferred is coating withsolutions adapted to build a hard candy layer. Both sugar and sugaralcohols may be used for this purpose together with high intensitysweeteners, colorants, flavoring agents, binders and other conventionaladditives. When the combination of stain removing agents is provided inthe coating of a chewing gum composition, a solution of the stainremoving agents is preferably, alternately applied with the flavoringagent.

The sweetener may be present in an amount of from about 30% to 80% byweight of the coating syrup. A binder such as magnesium stearate may beadded to the coating syrup in an amount of from about 1% to 15% byweight of the coating syrup to enhance or promote adhesion. Optionally,minor amounts of conventional additives may also be present. Thesweeteners suitable for use in the coating syrup comprise sugarlesssweeteners such as the polyhydric alcohols, e.g., xylitol, sorbitol,mannitol, and mixtures, thereof; as well as maltitol, isomaltitol,hydrogenated starch hydrolysates, and hydrogenated glucose syrups. Mono,di- and polysaccharide may also be included. For example, sugars such assucrose, fructose, glucose, galactose and maltose may also be employedas a sweetener. Other sweeteners suitable for use in the coating syrupinclude, but are not limited to free saccharin acid, water soluble saltsof saccharin, cyclamate salts, palatinit dihydrochalcones, glycyrrhizin,L-aspartyl-L-phenylalanine methyl ester, amino acid based sweeteners,talin, steviosides, dihydrochalcone compounds, acesulfame salts andmixtures thereof.

Other ingredients may be added in minor amounts to the coating syrup andinclude moisture absorbing compounds, anti-adherent compounds,dispersing agents and film forming agents. The moisture absorbingcompounds suitable for use in the coating syrups include mannitol ordicalcium phosphate. Examples of useful anti-adherent compounds, whichmay also function as filler, include talc, magnesium trisilicate andcalcium carbonate. These ingredients may be employed in amounts of about0.5% to 5% by weight of the syrup. Examples of dispersing agents, whichmay be employed in the coating syrup, include titanium dioxide, talc orother anti-adherent compounds as set forth above.

The coating syrup can be heated and a portion thereof deposited on thecores. Usually a single deposition of the coating syrup is notsufficient to provide the desired amount or thickness of coating and itusually will be necessary to apply second, third or more coats of thecoating syrup in order to build up the weight and thickness of thecoating to desired levels with layers allowed to dry in-between coats.

In some embodiments of the chewing gum composition, the coolingcompositions can be added to the coating. They are preferably appliedsubsequent to the syrup coating. Further details regarding thepreparation of chewing gum compositions can be found in Skuse's CompleteConfectioner (13th Edition) (1957) including pp. 41-71, 133-144, and255-262; and Sugar Confectionery Manufacture (2nd Edition) (1995), E. B.Jackson, Editor, pp. 258-286, the content of which is incorporatedherein by reference.

Confectionary Compositions

The present description also encompasses confectionery productscontaining a composition of individual agents that in total impart aphysiological effect that can be substantially cooling. Confectionerycompositions include compressed tablets such as mints, hard boiledcandies, nougats, gels, center fill confections, fondants, panning goodsand other compositions falling within the generally accepted definitionof confectionery compositions.

Confectionery compositions in the form of pressed tablets such as mintsmay generally be made by combining finely sifted sugar or sugarsubstitute, flavoring agent (e.g. peppermint flavor), bulking agent suchas gum arabic, and an optional coloring agent. The flavoring agent andthe bulking agent are combined and then gradually the sugar or sugarsubstitute are added along with a coloring agent, if needed.

The product then can be granulated by passing through a sieve of desiredmesh size (e.g. 12 mesh) and then dried at typically 55° C. to 60° C.The resulting powder can be fed into a tableting machine fitted with alarge size punch and the resulting pellets are broken into granules andthen pressed.

High boiled candies typically contain sugar or sugar substitute,glucose, water, flavoring agent and optional coloring agent. The sugarcan be dissolved in the water and glucose can be then added. The mixturecan be brought to a boil. The resulting liquid to which may previouslyhave been added a coloring agent can be poured onto an oiled slab andcooled. The flavoring agent then can be added and kneaded into thecooled mass. The resulting mixture then can be fed to a drop rollerassembly known in the art to form the final hard candy shape.

A nougat composition typically includes two principal ingredients, ahigh boiled candy and a frappe. By way of example, egg albumen orsubstitute thereof can be combined with water and whisked to form alight foam. Sugar and glucose are added to water and boiled typically atabout 130° C. to 140° C. and the resulting boiled product can be pouredinto a mixing machine and beat until creamy. The beaten albumen andflavoring agent are combined with the creamy product and the combinationcan be thereafter thoroughly mixed.

Further details regarding the preparation of confectionery compositionscan be found in Skuse's Complete Confectioner (13th Edition) (1957)including pp. 41-71, 133-144, and 255-262; and Sugar ConfectioneryManufacture (2nd Edition) (1995), E. B. Jackson, Editor, pp. 129-168,169-188, 189-216, 218-234, and 236-258, the content of which isincorporated herein by reference.

Additional Components

In addition to the cooling compositions described herein, the chewinggum and confectionery compositions may include a variety of optionaladditives, such as, but not limited to, sensates, mouth moisteningagents, potentiators, sweeteners, effervescent agents, acids andflavors.

Flavorants

In some embodiments, flavorants may include those flavors known to theskilled artisan, such as natural and artificial flavors. Theseflavorings may be chosen from synthetic flavor oils and flavoringaromatics and/or oils, oleoresins and extracts derived from plants,leaves, flowers, fruits, and so forth, and combinations thereof.Nonlimiting representative flavor oils include spearmint oil, cinnamonoil, oil of wintergreen (methyl salicylate), peppermint oil, Japanesemint oil, clove oil, bay oil, anise oil, eucalyptus oil, thyme oil,cedar leaf oil, oil of nutmeg, allspice, oil of sage, mace, oil ofbitter almonds, and cassia oil. Also useful flavorings are artificial,natural and synthetic fruit flavors such as vanilla, and citrus oilsincluding lemon, orange, lime, grapefruit, yazu, sudachi, and fruitessences including apple, pear, peach, grape, blueberry, strawberry,raspberry, cherry, plum, pineapple, apricot, banana, melon, apricot,ume, cherry, raspberry, blackberry, tropical fruit, mango, mangosteen,pomegranate, papaya and so forth. Other potential flavors whose releaseprofiles can be managed include a milk flavor, a butter flavor, a cheeseflavor, a cream flavor, and a yogurt flavor; a vanilla flavor; tea orcoffee flavors, such as a green tea flavor, a oolong tea flavor, a teaflavor, a cocoa flavor, a chocolate flavor, and a coffee flavor; mintflavors, such as a peppermint flavor, a spearmint flavor, and a Japanesemint flavor; spicy flavors, such as an asafetida flavor, an ajowanflavor, an anise flavor, an angelica flavor, a fennel flavor, anallspice flavor, a cinnamon flavor, a camomile flavor, a mustard flavor,a cardamom flavor, a caraway flavor, a cumin flavor, a clove flavor, apepper flavor, a coriander flavor, a sassafras flavor, a savory flavor,a Zanthoxyli Fructus flavor, a perilla flavor, a juniper berry flavor, aginger flavor, a star anise flavor, a horseradish flavor, a thymeflavor, a tarragon flavor, a dill flavor, a capsicum flavor, a nutmegflavor, a basil flavor, a marjoram flavor, a rosemary flavor, a bayleafflavor, and a wasabi (Japanese horseradish) flavor; alcoholic flavors,such as a wine flavor, a whisky flavor, a brandy flavor, a rum flavor, agin flavor, and a liqueur flavor; floral flavors; and vegetable flavors,such as an onion flavor, a garlic flavor, a cabbage flavor, a carrotflavor, a celery flavor, mushroom flavor, and a tomato flavor. Theseflavoring agents may be used in liquid or solid form and may be usedindividually or in admixture. Commonly used flavors include mints suchas peppermint, menthol, spearmint, artificial vanilla, cinnamonderivatives, and various fruit flavors, whether employed individually orin admixture. Flavors may also provide breath freshening properties,particularly the mint flavors when used in combination with the coolingagents, described herein below.

In some embodiments, other flavorings include aldehydes and esters suchas cinnamyl acetate, cinnamaldehyde, citral diethylacetal, dihydrocarvylacetate, eugenyl formate, p-methylamisol, and so forth may be used.Generally any flavoring or food additive such as those described inChemicals Used in Food Processing, publication 1274, pages 63-258, bythe National Academy of Sciences, may be used. This publication isincorporated herein by reference. These may include natural as well assynthetic flavors.

Further examples of aldehyde flavorings include but are not limited toacetaldehyde (apple), benzaldehyde (cherry, almond), anisic aldehyde(licorice, anise), cinnamic aldehyde (cinnamon), citral, i.e.,alpha-citral (lemon, lime), neral, i.e., beta-citral (lemon, lime),decanal (orange, lemon), ethyl vanillin (vanilla, cream), heliotrope,i.e., piperonal (vanilla, cream), vanillin (vanilla, cream), alpha-amylcinnamaldehyde (spicy fruity flavors), butyraldehyde (butter, cheese),valeraldehyde (butter, cheese), citronellal (modifies, many types),decanal (citrus fruits), aldehyde C-8 (citrus fruits), aldehyde C-9(citrus fruits), aldehyde C-12 (citrus fruits), 2-ethyl butyraldehyde(berry fruits), hexenal, i.e., trans-2 (berry fruits), tolyl aldehyde(cherry, almond), veratraldehyde (vanilla), 2,6-dimethyl-5-heptenal,.e., melonal (melon), 2,6-dimethyloctanal (green fruit), and 2-dodecenal(citrus, mandarin), cherry, grape, blueberry, blackberry, strawberryshortcake, and mixtures thereof.

In some embodiments, flavoring agents are used at levels that provide aperceptible sensory experience i.e. at or above their threshold levels.In other embodiments, flavoring agents are used at levels below theirthreshold levels such that they do not provide an independentperceptible sensory experience. At sub-threshold levels, the flavoringagents may provide an ancillary benefit such as flavor enhancement orpotentiation.

In some embodiments, a flavoring agent may be employed in either liquidform and/or dried form. When employed in the latter form, suitabledrying means such as spray drying the liquid may be used. Alternatively,the flavoring agent may be absorbed onto water soluble materials, suchas cellulose, starch, sugar, maltodextrin, gum arabic and so forth ormay be encapsulated. In still other embodiments, the flavoring agent maybe adsorbed onto silicas, zeolites, and the like.

In some embodiments, the flavoring agents may be used in many distinctphysical forms. Without being limited thereto, such physical formsinclude free forms, such as spray dried, powdered, beaded forms,encapsulated forms, and mixtures thereof.

Illustrations of the encapsulation of flavors as well as otheradditional components can be found in the examples provided herein.Typically, encapsulation of a component will result in a delay in therelease of the predominant amount of the component during consumption ofa confectionery composition that includes the encapsulated component(e.g., as part of a delivery system added as an ingredient to thechewing confectionery composition). In some embodiments, the releaseprofile of the ingredient (e.g., the flavor, sweetener, etc.) can bemanaged by managing various characteristics of the ingredient, deliverysystem containing the ingredient, and/or the confectionery compositioncontaining the delivery system and/or how the delivery system is made.For example, characteristics might include one or more of the following:tensile strength of the delivery system, water solubility of theingredient, water solubility of the encapsulating material, watersolubility of the delivery system, ratio of ingredient to encapsulatingmaterial in the delivery system, average or maximum particle size ofingredient, average or maximum particle size of ground delivery system,the amount of the ingredient or the delivery system in the confectionerycomposition, ratio of different polymers used to encapsulate one or moreingredients, hydrophobicity of one or more polymers used to encapsulateone or more ingredients, hydrophobicity of the delivery system, the typeor amount of coating on the delivery system, the type or amount ofcoating on an ingredient prior to the ingredient being encapsulated,etc.

Sweetening Ingredients

The sweeteners involved may be selected from a wide range of materialsincluding water-soluble sweeteners, water-soluble artificial sweeteners,water-soluble sweeteners derived from naturally occurring water-solublesweeteners, dipeptide based sweeteners, and protein based sweeteners,including mixtures thereof. Without being limited to particularsweeteners, representative categories and examples include:

(a) water-soluble sweetening agents such as dihydrochalcones, monellin,steviosides, lo han quo, glycyrrhizin, dihydroflavenol, and sugaralcohols such as sorbitol, mannitol, maltitol, xylitol, erythritol, andL-aminodicarboxylic acid aminoalkenoic acid ester amides, such as thosedisclosed in U.S. Pat. No. 4,619,834, which disclosure is incorporatedherein by reference, and mixtures thereof;

(b) water-soluble artificial sweeteners such as soluble saccharin salts,i.e., sodium or calcium saccharin salts, cyclamate salts, the sodium,ammonium or calcium salt of3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide, the potassiumsalt of 3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide(Acesulfame-K), the free acid form of saccharin, and mixtures thereof;

(c) dipeptide based sweeteners, such as L-aspartic acid derivedsweeteners, such as L-aspartyl-L-phenylalanine methyl ester (Aspartame),N-[N-(3,3-dimethylbutyl)-L-α-aspartyl]-L-phenylalanine 1-methyl ester(Neotame), and materials described in U.S. Pat. No. 3,492,131,L-alphaaspartyl-N-(2,2,4,4-tetramethyl-3-thietanyl)-D-alaninamidehydrate (Alitame), methyl esters of L-aspartyl-L-phenylglycerine andL-aspartyl-L-2,5-dihydrophenylglycine,L-aspartyl-2,5-dihydro-L-phenylalanine;L-aspartyl-L-(1-cyclohexen)-alanine, and mixtures thereof;

(d) water-soluble sweeteners derived from naturally occurringwater-soluble sweeteners, such as chlorinated derivatives of ordinarysugar (sucrose), e.g., chlorodeoxysugar derivatives such as derivativesof chlorodeoxysucrose or chlorodeoxygalactosucrose, known, for example,under the product designation of Sucralose or Splenda™; examples ofchlorodeoxysucrose and chlorodeoxygalactosucrose derivatives include butare not limited to: 1-chloro-1′-deoxysucrose;4-chloro-4-deoxy-alpha-D-galactopyranosyl-alpha-D-fructofuranoside, or4-chloro-4-deoxygalactosucrose;4-chloro-4-deoxy-alpha-D-galactopyranosyl-1-chloro-1-deoxy-beta-D-fructofuranoside,or 4,1′-dichloro-4,1′-dideoxygalactosucrose; 1′,6′-dichloro1′,6′-dideoxysucrose;4-chloro-4-deoxy-alpha-D-galactopyranosyl-1,6-dichloro-1,6-dideoxy-beta-D-fructofuranoside,or 4,1′,6′-trichloro-4,1′,6′-trideoxygalactosucrose;4,6-dichloro-4,6-dideoxy-alpha-D-galactopyranosyl-6-chloro-6-deoxy-beta-D-fructofuranoside,or 4,6,6′-trichloro-4,6,6′-trideoxygalactosucrose;6,1′,6′-trichloro-6,1′,6′-trideoxysucrose;4,6-dichloro-4,6-dideoxy-alpha-D-galacto-pyranosyl-1,6-dichloro-1,6-dideoxy-beta-D-fructo-furanoside,or 4,6,1′,6′-tetrachloro 4,6,1′,6′-tetradeoxygalacto-sucrose; and4,6,1′,6′-tetradeoxy-sucrose, and mixtures thereof;

(e) protein based sweeteners such as thaumaoccous danielli (Thaumatin Iand II) and talin; and

-   the sweetener monatin    (2-hydroxy-2-(indol-3-ylmethyl)-4-aminoglutaric acid) and its    derivatives.

The intense sweetening agents may be used in many distinct physicalforms well-known in the art to provide an initial burst of sweetnessand/or a prolonged sensation of sweetness. Without being limitedthereto, such physical forms include free forms, spray dried forms,powdered forms, beaded forms, encapsulated forms, and mixtures thereof.In one embodiment, the sweetener is a high intensity sweetener such asaspartame, sucralose, and acesulfame potassium (e.g., Ace-K oracesulfame-K).

In some embodiments, the sweetener may be a polyol. Polyols can include,but are not limited to glycerol, sorbitol, maltitol, maltitol syrup,mannitol, isomalt, erythritol, xylitol, hydrogenated starchhydrolysates, polyglycitol syrups, polyglycitol powders, lactitol, andcombinations thereof.

The active component (e.g., sweetener), which is part of the deliverysystem, may be used in amounts necessary to impart the desired effectassociated with use of the active component (e.g., sweetness). Ingeneral, an effective amount of intense sweetener may be utilized toprovide the level of sweetness desired, and this amount may vary withthe sweetener selected. The intense sweetener may be present in amountsfrom about 0.001% to about 3%, by weight of the composition, dependingupon the sweetener or combination of sweeteners used. The exact range ofamounts for each type of sweetener may be selected by those skilled inthe art.

Sensate Ingredients

In addition to cooling agents, as described above, sensate compounds caninclude warming agents, tingling agents, effervescent agents, andcombinations thereof.

In some embodiments, warming components may be selected from a widevariety of compounds known to provide the sensory signal of warming tothe user. These compounds offer the perceived sensation of warmth,particularly in the oral cavity, and often enhance the perception offlavors, sweeteners and other organoleptic components. In someembodiments, useful warming compounds can include vanillyl alcoholn-butylether (TK-1000) supplied by Takasago Perfumary Company Limited,Tokyo, Japan, vanillyl alcohol n-propylether, vanillyl alcoholisopropylether, vanillyl alcohol isobutylether, vanillyl alcoholn-aminoether, vanillyl alcohol isoamyleather, vanillyl alcoholn-hexyleather, vanillyl alcohol methylether, vanillyl alcoholethylether, gingerol, shogaol, paradol, zingerone, capsaicin,dihydrocapsaicin, nordihydrocapsaicin, homocapsaicin,homodihydrocapsaicin, ethanol, isopropyl alcohol, iso-amylalcohol,benzyl alcohol, glycerine, and combinations thereof.

In some embodiments, a tingling sensation can be provided. One suchtingling sensation is provided by adding jambu, oleoresin, or spilantholto some examples. In some embodiments, alkylamides extracted frommaterials such as jambu or sanshool can be included. Additionally, insome embodiments, a sensation is created due to effervescence. Sucheffervescence is created by combining an alkaline material with anacidic material. In some embodiments, an alkaline material can includealkali metal carbonates, alkali metal bicarbonates, alkaline earth metalcarbonates, alkaline earth metal bicarbonates and mixtures thereof. Insome embodiments, an acidic material can include acetic acid, adipicacid, ascorbic acid, butyric acid, citric acid, formic acid, fumaricacid, glyconic acid, lactic acid, phosphoric acid, malic acid, oxalicacid, succinic acid, tartaric acid, aspartic acid, benzoic acid,caffeotannic acid, iso-citric acid, citramalic acid, galacturonic acid,glucuronic acid, glyceric acid, glycolic acid, ketoglutaric acid,a-ketoglutaric acid, lactoisocitric acid, oxalacetic acid, pyruvic acid,quinic acid, shikimic acid, succinic acid, tannic acid, hydroxyaceticacid, suberic acid, sebacic acid, azelaic acid, pimelic acid, capriccid, and combinations thereof. Examples of “tingling” type sensates canbe found in U.S. Pat. No. 6,780,443, the entire contents of which areincorporated herein by reference for all purposes.

Sensate components may also be referred to as “trigeminal stimulants”such as those disclosed in U.S. Patent Application No. 2005/0202118,which is incorporated herein by reference. Trigeminal stimulants aredefined as an orally consumed product or agent that stimulates thetrigeminal nerve. Examples of cooling agents which are trigeminalstimulants include menthol, WS-3, N-substituted p-menthane carboxamide,acyclic carboxamides including WS-23, WS-5, WS-14, methyl succinate, andmenthone glycerol ketals. Trigeminal stimulants can also includeflavors, tingling agents, Jambu extract, vanillyl alkyl ethers, such asvanillyl n-butyl ether, spilanthol, Echinacea extract, Northern PricklyAsh extract, capsaicin, capsicum oleoresin, red pepper oleoresin, blackpepper oleoresin, piperine, ginger oleoresin, gingerol, shoagol,cinnamon oleoresin, cassia oleoresin, cinnamic aldehyde, eugenol, cyclicacetal of vanillin and menthol glycerin ether, unsaturated amides, andcombinations thereof. Other cooling compounds can include derivatives of2,3-dimethyl-2-isopropylbutyric acid such as those disclosed in U.S.Pat. No. 7,030,273, which is incorporated herein by reference.

In addition to trigeminal nerve stimulants and cooling compounds, acooling sensation can be provided by materials exhibiting a negativeheat of solution including, but not limited to, polyols such as xylitol,erythritol, dextrose, and sorbitol, and combinations thereof.

In some embodiments, sensate components are used at levels that providea perceptible sensory experience i.e. at or above their thresholdlevels. In other embodiments, sensate components are used at levelsbelow their threshold levels such that they do not provide anindependent perceptible sensory experience. At subthreshold levels, thesensates may provide an ancillary benefit such as flavor or sweetnessenhancement or potentiation.

Effervescing System Ingredients

An effervescent system may include one or more edible acids and one ormore edible alkaline materials. The edible acid(s) and the ediblealkaline material(s) may react together to generate effervescence.

In some embodiments, the alkaline material(s) may be selected from, butis not limited to, alkali metal carbonates, alkali metal bicarbonates,alkaline earth metal carbonates, alkaline earth metal bicarbonates, andcombinations thereof. The edible acid(s) may be selected from, but isnot limited to, citric acid, phosphoric acid, tartaric acid, malic acid,ascorbic acid, and combinations thereof. In some embodiments, aneffervescing system may include one or more other ingredients such as,for example, carbon dioxide, oral care ingredients, flavorants, etc.

For examples of use of an effervescing system in a chewingconfectionery, refer to U.S. Provisional Patent No. 60/618,222 filedOct. 13, 2004, and entitled “Effervescent Pressed Confectionery TabletCompositions,” the contents of which are incorporated herein byreference for all purposes. Other examples can be found in U.S. Pat. No.6,235,318, the contents of which are incorporated herein by referencefor all purposes.

Potentiator Ingredients

Potentiators can consist of materials that may intensify, supplement,modify or enhance the taste and/or aroma perception of an originalmaterial without introducing a characteristic taste and/or aromaperception of their own. In some embodiments, potentiators designed tointensify, supplement, modify, or enhance the perception of flavor,sweetness, tartness, umami, kokumi, saltiness and combinations thereofcan be included.

In some embodiments, examples of suitable potentiators, also known astaste potentiators include, but are not limited to, neohesperidindihydrochalcone, optically active S-alkyl 2-methyl butane thioatecompounds such as those disclosed in PCT Application Number WO2007/032262 to Ogura et al, which is incorporated in its entirety hereinby reference, chlorogenic acid, alapyridaine, cynarin, miraculin,glupyridaine, pyridinium-betain compounds, glutamates, such asmonosodium glutamate and monopotassium glutamate, neotame, thaumatin,tagatose, trehalose, salts, such as sodium chloride, monoammoniumglycyrrhizinate, vanilla extract (in ethyl alcohol), sugar acids,potassium chloride, sodium acid sulfate, hydrolyzed vegetable proteins,hydrolyzed animal proteins, yeast extracts, adenosine monophosphate(AMP), glutathione, nucleotides, such as inosine monophosphate, disodiuminosinate, xanthosine monophosphate, guanylate monophosphate,alapyridaine (N-(1-carboxyethyl)-6-(hydroxymethyl)pyridinium-3-ol innersalt, compositions comprising 5′-nucleotides such as those disclosed inUS 2006/0078972 to Noordam et al, which is incorporated in its entiretyherein by reference, sugar beet extract (alcoholic extract), sugarcaneleaf essence (alcoholic extract), curculin, strogin, mabinlin, gymnemicacid, hydroxybenzoic acids, 3-hydrobenzoic acid, 2,4-dihydrobenzoicacid, citrus aurantium, vanilla oleoresin, sugarcane leaf essence,maltol, ethyl maltol, vanillin, licorice glycyrrhizinates, compoundsthat respond to the TRPM5 ion channel that mediates taste receptors forsweet, bitter, and savory tastes as disclosed in U.S. Patent ApplicationNumber 2005/0019830 to Penner et al, which is incorporated in itsentirety herein by reference, pyridinium betain compounds as disclosedin U.S. Pat. No. 7,175,872 to Hofmann et al, which is incorporated inits entirety herein by reference, compounds that respond to G-proteincoupled receptors (T2Rs and T1Rs) and taste potentiator compositionsthat impart kokumi, as disclosed in U.S. Pat. No. 5,679,397 to Kuroda etal., which is incorporated in its entirety herein by reference. “Kokumi”refers to materials that impart “mouthfulness” and “good body”.

Sweetener potentiators, which are a type of taste potentiator, enhancethe taste of sweetness. In some embodiments, exemplary sweetenerpotentiators include, but are not limited to, monoammoniumglycyrrhizinate, licorice glycyrrhizinates, citrus aurantium,alapyridaine, alapyridaine(N-(1-carboxyethyl)-6-(hydroxymethyl)pyridinium-3-ol) inner salt,miraculin, curculin, strogin, mabinlin, gymnemic acid, cynarin,glupyridaine, pyridinium-betain compounds, sugar beet extract, neotame,thaumatin, neohesperidin dihydrochalcone, hydroxybenzoic acids,tagatose, trehalose, maltol, ethyl maltol, vanilla extract, vanillaoleoresin, vanillin, sugar beet extract (alcoholic extract), sugarcaneleaf essence (alcoholic extract), compounds that respond to G-proteincoupled receptors (T2Rs and T1Rs) and combinations thereof.

Additional examples of potentiators for the enhancement of salt tasteinclude acidic peptides, such as those disclosed in U.S. Pat. No.6,974,597, herein incorporated by reference. Acidic peptides includepeptides having a larger number of acidic amino acids, such as asparticacid and glutamic acid, than basic amino acids, such as lysine, arginineand histidine. The acidic peptides are obtained by peptide synthesis orby subjecting proteins to hydrolysis using endopeptidase, and ifnecessary, to deamidation. Suitable proteins for use in the productionof the acidic peptides or the peptides obtained by subjecting a proteinto hydrolysis and deamidation include plant proteins, (e.g. wheatgluten, corn protein (e.g., zein and gluten meal), soybean proteinisolate), animal proteins (e.g., milk proteins such as milk casein andmilk whey protein, muscle proteins such as meat protein and fish meatprotein, egg white protein and collagen), and microbial proteins (e.g.,microbial cell protein and polypeptides produced by microorganisms).

The sensation of warming or cooling effects may also be prolonged withthe use of a hydrophobic sweetener as described in U.S. PatentApplication Publication 2003/0072842 A1 which is incorporated in itsentirety herein by reference. For example, such hydrophobic sweetenersinclude those of the formulae I-XI as set forth below:

wherein X, Y and Z are selected from the group consisting of CH₂, O andS;

wherein X and Y are selected from the group consisting of S and O;

wherein X is S or O; Y is O or CH₂; Z is CH₂, SO₂ or S; R is OCH₃, OH orH; R¹ is SH or OH and R² is H or OH;

wherein X is C or S; R is OH or H and R¹ is OCH₃ or OH;

wherein R, R² and R³ are OH or H and R¹ is H or COOH;

wherein X is O or CH₂ and R is COOH or H;

wherein R is CH₃CH₂, OH, N (CH3)₂ or Cl;

Perillartine may also be added as described in U.S. Pat. No. 6,159,509also

incorporated in its entirety herein by reference.

Food Acid Ingredients

Acids can include, but are not limited to acetic acid, adipic acid,ascorbic acid, butyric acid, citric acid, formic acid, fumaric acid,glyconic acid, lactic acid, phosphoric acid, malic acid, oxalic acid,succinic acid, tartaric acid, aspartic acid, benzoic acid, caffeotannicacid, iso-citric acid, citramalic acid, galacturonic acid, glucuronicacid, glyceric acid, glycolic acid, ketoglutaric acid, a-ketoglutaricacid, lactoisocitric acid, oxalacetic acid, pyruvic acid, quinic acid,shikimic acid, succinic acid, tannic acid, hydroxyacetic acid, subericacid, sebacic acid, azelaic acid, pimelic acid, capric cid, andcombinations thereof.

Mouth Moistening Ingredients

Mouth moisteners can include, but are not limited to, saliva stimulatorssuch as acids and salts and combinations thereof. In some embodiments,acids can include acetic acid, adipic acid, ascorbic acid, butyric acid,citric acid, formic acid, fumaric acid, glyconic acid, lactic acid,phosphoric acid, malic acid, oxalic acid, succinic acid, tartaric acidand combinations thereof.

Mouth moisteners can also include hydrocolloid materials that hydrateand may adhere to oral surface to provide a sensation of mouthmoistening. Hydrocolloid materials can include naturally occurringmaterials such as plant exudates, seed gums, and seaweed extracts orthey can be chemically modified materials such as cellulose, starch, ornatural gum derivatives. In some embodiments, hydrocolloid materials caninclude pectin, gum arabic, acacia gum, alginates, agar, carageenans,guar gum, xanthan gum, locust bean gum, gelatin, gellan gum, cassia gum,galactomannans, tragacanth gum, karaya gum, curdlan, konjac, chitosan,xyloglucan, beta glucan, furcellaran, gum ghatti, tamarin, bacterialgums, and combinations thereof. Additionally, in some embodiments,modified natural gums such as propylene glycol alginate, carboxymethyllocust bean gum, low methoxyl pectin, and their combinations can beincluded. In some embodiments, modified celluloses can be included suchas microcrystalline cellulose, carboxymethlcellulose (CMC),methylcellulose (MC), hydroxypropylmethylcellulose (HPCM), andhydroxypropylcellulose (MPC), and combinations thereof.

Similarly, humectants which can provide a perception of mouth hydrationcan be included. Such humectants can include, but are not limited toglycerol, sorbitol, polyethylene glycol, erythritol, and xylitol.Additionally, in some embodiments, fats can provide a perception ofmouth moistening. Such fats can include medium chain triglycerides,vegetable oils, fish oils, mineral oils, and combinations thereof.

Mouth moisteners can also include pellitorine extracts, extracts ofAnacyclus pyrethrum, trans-pellitorin,N-isobutyl-trans-2-trans-4-decadienamide, alkadienamides includingN-isobutyl-E2, E4-decadienamide; N-isobutyl-E2, E4-undecadienamide;N-pyrollidyl-E2, E4-decadienamide; N-piperidl-E2, E4-decadienamdie, orcombinations thereof as disclosed in U.S. Patent Application No.2007/0075368 which is incorporated in its entirety herein by reference;blends of n-isobutyldeca-trans-2-trans-4-dienamide with food acids asdisclosed in U.S. Patent Application No. 2006/0204551 which isincorporated in its entirety herein by reference; blends of compoundsaccording to formula (I): wherein R₁ represents C1-C2 n-alkyl; R₂ is2-methyl-1-propyl and R₃ is hydrogen, or R₂ and R₃ taken together is amoiety having the formula —(CH₂)_(n)— wherein n is 4 or 5, or mixturesthereof with cooling compounds as disclosed in U.S. Patent ApplicationNo. 2007/0036838 to Keenan et al, which is incorporated in its entiretyherein by reference.

Quantitative Descriptive Analysis

Many sensory test methods such as descriptive analysis depend upon thejudgments of panelists about the perceived strength of individualsensory characteristics in a product. These perceived intensityestimates are often given as scale numbers or choices on a rating scale.Judgments are often made relative to some frame of reference, which issometimes explicit in the training of the panel. However, humanjudgments tend to shift as a function of the immediate context, and theset of products evaluated within a sensory test session can skew theratings of an individual judge. There can be a stabilizing effect oftraining and reference standards in reducing such context effects andthe resistance of different scaling methods to contextual shifting.

One text covering all the basic techniques of sensory testing is SensoryEvaluation of Food: Principles & Practices, by Harry T. Lawless andHildegarde Heymann, the disclosure of which is herein incorporated byreference. Statistics used in sensory evaluation are demonstrated asintegrated applications in the context of appropriate sensory methodsand are also presented as stand-alone material in appendices.Statistical applications are tailored to common analyses encountered tosensory work, together with instructions on how tests should beconducted. One exemplary application of the principles of quantitativedescriptive analysis with respect to milk products is provided byChapman et al., J. Dairy Science 84:12-20 (2001).

A panel of respondents may be assembled for sensory evaluation.Attribute terms for evaluation of samples are selected. Normally, ballotdevelopment and respondent training is carried out initially.Descriptive terms are developed for major sensory attribute categories.Exemplary attribute qualities include aroma, flavor, texture,aftertaste, sweetness, etc. Attributes are quantified with an intensityscale of from, e.g. 0 to 10; where 0 indicates that the attribute is notdetected and 10 indicates the attribute is extremely strong. Overallquality rating may be measured with a scale of from, e.g. 1 to 10 whereless than 6 is considered “poor,” 6 to 7 is “fair,” and 8 to 10 is“good.”

Physical reference standards are determined by a panel consensus so thatproper descriptive language may be developed. Panelists may be trainedin evaluating certain samples until a consensus is attained.

Overall quality ratings and quantified intensity ratings may be analyzedwith such programs as Minitab ver. 12 or SAS ver. 6.11. Descriptivestatistical measures may be calculated for all attributes. Analysis ofvariance may be performed on each attribute using a randomized blockdesign for balanced data with panelists as repeated measures asdescribed by Ott, “Analysis of variance for some standard experimentaldesigns,” pp. 844-856 in An Introduction to Statistical Methods and DataAnalysis. Wadsworth Publishing. Belmont, Calif. Where F-test indicates asignificant difference between treatment means, Tukey paired comparisonsand orthogonal comparisons may be used to determine where the means aredifferent. Significance of differences may be defined as P less than0.05. Principal components analysis (PCA) may be applied with the factoranalysis described by Lawless and Heymann, 1998, pp. 606-608 in SensoryEvaluation of Food: Principles and Practices. Chapman & Hall, New York,1998. PCA may be applied to the attributes. Attributes may be omitted ifthe values are consistently low indicating that the attribute is notoften present, if the attribute has a high standard deviation or if theattribute is highly correlated to another attribute. Kaiser's criterionmay be applied (eigen value greater than 1) to determine the number offinal factors from the initial ones as described by Massart et al.,“Principal components and factor analysis,” pp. 339-369 in Chemometrics:A Textbook. Elsevier, Amsterdam, 1988. To facilitate the interpretationof results, the factors may be orthogonally rotated leading touncorrelated factors following the Varimax method described by Massartet al., supra.

The overall quality ratings (dependent variables) may be modeled as afunction of the Varimax rotated PC scores for the products (independentvariables). Models may be constructed using ordinary least squares(OLS), principal components regression (PCR), and partial least squaresregression (PLS) routines in SCAN for Windows Release 1.1. PCR and PLSmodels may be calculated with, for instance, one to four components. Ineach case, the best fit equations (those with the highest R²) and thosewith the best predictive ability (lowest residual predictive sum ofsquares, or residual PRESS) are obtained.

Further, respondents can score each product at three time points; oneminute, fifteen minutes, and thirty minutes for overall liking andintensity of four attributes: flavor, sweetness, cooling/warming andtexture. A fifteen minute rest period can be provided between eachproduct allowing for palate cleansing. The tests can be performedgenerally according to the criterion set forth above. Such statisticalprocesses as set forth above may be used to analyze the data collected.

The present cooling compositions and methods will now be illustrated ingreater detail with reference to Examples in view of ComparativeExamples, but it should be understood that the methods and compositionsare not limited thereto. Unless otherwise noted, all the percents are byweight.

In some embodiments, cooling compositions can be formulated to contain amenthyl glutarate ester in the following amounts expressed as weightpercent. Additionally, the cooling compositions can be coupled with aflavor composition as indicated. WS-3 and WS-23 are shown together toindicate that they can be used interchangeably. TABLE 1 Example Number %w/w Component 1 2 3 4 5 6 7 8 9 Menthyl 5-60 5-60 5-60 5-60 glutarateMenthyl 5-60 5-60 5-60 5-60 lactate Menthyl 5-60 5-60 5-60 5-60succinate Menthyl 5-60 5-60 5-60 acetate WS3 or 5-50 5-50 5-50 5-50 WS23WS5 5-50 Ice 6000 5-50 Ice 10000 5-50 Ice 11000 5-50 Menthol 15-85 15-85  15-85  15-85  15-85  Isopulegol 2-50 p-menthane 2-50 3,8 diol

TABLE 2 Chewing Gum Compositions 1. Gum Base 20-50% Sugar 35-80% GlucoseSyrup 8-25% Sweetener 0.01-1.5% Lecithin 0.2-1.2% Glycerin 1-8% Color0.01-0.05% Peppermint Flavor 1.2-2.5% Cooling Composition 0.2-1.2% 2.Gum Base 20-50% Sugar 35-80% Glucose Syrup 8-25% Sweetener 0.01-1.5%Lecithin 0.2-1.2% Glycerin 1-8% Color 0.01-0.05% Wintergreen Flavor0.9-2.3% Peppermint Flavor 0.5-1.5% Cooling Composition 0.2-1.2% 3. GumBase 20-50% Sugar 35-80% Glucose Syrup 8-25% Sweetener 0.01-1.5%Lecithin 0.2-1.2% Glycerin 1-8% Color 0.01-0.05% Spearmint Flavor1.2-2.5% Cooling Composition 0.2-1.2% 4. Gum Base 20-50% Sugar 35-80%Glucose Syrup 8-25% Sweetener 0.01-1.5% Lecithin 0.2-1.2% Glycerin 1-8%Color 0.01-0.05% Cinnamon Flavor 1.5-2.5% Cooling Composition 0.2-1.2%5. Gum Base 20-50% Sugar 35-80% Glucose Syrup 8-25% Sweetener 0.01-1.5%Lecithin 0.2-1.2% Glycerin 1-8% Color 0.01-0.05% Fruit Flavor 1.2-2.5%Cooling Composition 0.2-1.2% 6. Gum Base 20-50% Sorbitol Powder 35-80%Sweetener 0.01-1.5% Lecithin 0.2-1.2% Glycerin 3-15% Color 0.01-0.05%Peppermint Flavor 1.2-2.5% Cooling Composition 0.2-1.2% 7. Gum Base20-50% Mannitol Powder 35-80% Sweetener 0.01-1.5% Lecithin 0.2-1.2%Glycerin 3-15% Color 0.01-0.05% Peppermint Flavor 1.2-2.5% CoolingComposition 0.2-1.2% 8. Gum Base 20-50% Xylitol Powder 35-80% Sweetener0.01-1.5% Lecithin 0.2-1.2% Glycerin 3-15% Color 0.01-0.05% PeppermintFlavor 1.2-2.5% Cooling Composition 0.2-1.2% 9. Gum Base 20-50% XylitolPowder 35-80% Erythritol Powder 35-80% Sweetener 0.01-1.5% Lecithin0.2-1.2% Glycerin 3-15% Color 0.01-0.05% Peppermint Flavor 1.2-2.5%Cooling Composition 0.2-1.2%

TABLE 3 Confectionery Compositions % w/w Ingredient 10 11 12 13 14Sucrose 10%-35% 10%-30% 30%-60% Corn Syrup  2%-18% 10%-30% 60%-30% Water 3%-12%  3%-18%  3%-15%   10-30% 10%-20% Fat 0%-5% 0%-5% 0%-5%Hydrocolloids 0%-5% 0%-5% Lecithin   0%-0.5%   0%-0.6%   0%-0.6%  0%-0.6% GMS   0%-0.5%   0%-0.6%   0%-0.6%   0%-0.6% Hydrogenated 0%-6%Starch Hydrolysates Sorbitol  0%-35% Erythritol 0%-9%  0%-25% Xylitol 0%-60% Maltitol   0-60% Isomalt  0%-50%  0%-18% Mannitol   0-15% Flavor0.15%-3.0%  0.1%-1.5% 0.1%-1.5% 0.1%-1.5% 0.3%-3.0% Acid(s) 0.1%-1.5%0.1%-1.5% 0.1%-1.5% Color(s)   0%-0.15%   0%-0.12%   0%-0.12%   0%-0.12%  0%-0.12% Free Sweetener 0.1%-0.5%  0.01-0.2%  0.01-0.2% Encapsulated0.5%-7%   0.1%-2%   0.1%-2%   0.1%-2%   Sweetener Cooling   0.01-0.25%  0.01-0.25%   0.01-0.25% Composition Totals: 100 100 100 100 100

To prepare the confectionery products, portions of the sugar, cornsyrup, sorbitol, xylitol, erythritol, maltitol, mannitol, isomalt andwater are weighed, as indicated in Table 3 above, and combined. Themixture is heated to start boiling. While boiling the fat, lecithin, andGMS are added and mixed. The mixture is boiled to cook temperature. Thehydrocolloid is added in a pre-dissolved slurry format. The flavors,acids and colors are added. The mixture is mixed thoroughly and shapedinto the desired format.

Chewing Gum and Confectionary Compositions Providing a PhysiologicalCooling Sensation

In some embodiments, chewing gum and confectionaries will be preparedhaving some of the components provided below in amounts within thoseamounts recommended by the United Sattes government as not exceeding theamounts set forth below. The chewing gums and confectionary compositionswill demonstrate an ability to impart a physiological cooling sensation.TABLE 4 FEMA FEMA FEMA recomm. recomm. recomm. levels in levels in GRASlevels in HARD SOFT # Compound names GUM CANDY CANDY 2665 Menthol 1,100400 400 2667 Menthone 8.7 71 71 2668 Menthyl acetate 5.2 26 26 2962Isopulegol NA 23 23 3455 WS-3 1,200 10 10 3460 Isomenthone 600 60 603748 Menthyl Lactate 800 NA NA 3784 3-1-menthoxy- 4,000 500 500 propane-1,2-diol 3804 WS-23 3,000 50 NA 3805 1-menthol 20,000 2,000 NA ethyleneglycol carbonate 3806 1-menthol-1and2- 10,000 3,000 NA propylene glycolcarbonate 3807 1-menthone 1,2 800 NA 80 glycerol ketal 3808 d,1-menthone1,2 800 NA 80 glycerol ketal 3810 Mono-menthyl 3,750 600 600 succinate(physcool) 3992 d,1 menthol 20,000 2,000 2,000 propyleneglycol carbonate4006 L-monomenthyl 4,000 700 600 glutarate

From the foregoing description, various modifications and changes in thecompositions and methods will occur to those skilled in the art. Allsuch modifications coming within the scope of the appended claims areintended to be included therein.

All publications, including but not limited to patents and patentapplications, cited in this specification are herein incorporated byreference as if each individual publication were specifically andindividually fully set forth.

1. A cooling composition consisting essentially of: about 5% to about60% by weight menthyl glutarate; about 5% to about 50% by weight of atleast one cooling agent selected from the group consisting ofN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof; and about 15% to about 85% by weight menthol. 2.The cooling composition of claim 1, wherein said menthyl glutarate isselected from the group consisting of monomenthyl monomenthyl2-methylmaleatementhyl glutarate (FEMA 4006), monomenthyl glutarateester, dimenthyl glutarate ester, and a menthyl half acid esterderivative.
 3. A chewing gum composition comprising the coolingcomposition of claim
 1. 4. A confectionery composition comprising thecooling composition of claim
 1. 5. A cooling composition consistingessentially of: about 5% to about 60% by weight of at least two menthylesters; about 5% to about 50% by weight of at least one cooling agentselected from the group consisting of N-ethyl-p-menthane-3-carboxamide,trimethyl isopropyl butanamide and combinations thereof; and about 15%to about 85% by weight menthol.
 6. The cooling composition of claim 5,wherein said at least two menthyl esters are selected from the groupconsisting of monomenthyl monomenthyl 2-methylmaleatementhyl glutarate(FEMA 4006), monomenthyl glutarate ester, dimenthyl glutarate ester, amenthyl half acid ester derivative, menthyl acetate, 1-menthyl acetate,d,1-menthyl acetate, homomenthyl acetate, menthyl lactate, 1-menthyllactate, menthyl succinate, monomenthyl succinate, and combinationsthereof.
 7. A chewing gum composition comprising the cooling compositionof claim
 5. 8. A confectionery composition comprising the coolingcomposition of claim
 5. 9. A cooling composition comprising: about 5% toabout 60% by weight menthyl glutarate; about 5% to about 50% by weightof at least one cooling agent selected from the group consisting ofN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof; and at least about 75% by weight of the menthylglutarate and the at least one cooling agent, wherein said compositionis liquid at 25° C.
 10. The cooling composition of claim 9, furthercomprising menthol in amounts of about 15% to about 85% by weight of thecomposition.
 11. The cooling composition of claim 9, wherein saidmenthyl glutarate is selected from the group consisting monomenthyl2-methylmaleatementhyl glutarate (FEMA 4006), monomenthyl glutarateester, dimenthyl glutarate ester, and a menthyl half acid esterderivative.
 12. A chewing gum composition comprising the coolingcomposition of claim
 9. 13. A confectionery composition comprising thecooling composition of claim
 9. 14. A cooling composition comprising:about 5% to about 60% by weight of at least two menthyl esters; about 5%to about 50% by weight of at least one cooling agent selected from thegroup consisting of N-ethyl-p-menthane-3-carboxamide, trimethylisopropyl butanamide and combinations thereof; and at least about 75% byweight of the at least two menthyl esters and the at least one coolingagent, wherein said composition is liquid at 25° C.
 15. The coolingcomposition of claim 14, further comprising menthol in amounts of about15% to about 85% by weight of the composition.
 16. The coolingcomposition of claim 14, wherein said at least two menthyl esters areselected from the group consisting of monomenthyl monomenthyl2-methylmaleatementhyl glutarate (FEMA 4006), monomenthyl glutarateester, dimenthyl glutarate ester, a menthyl half acid ester derivative,menthyl acetate, 1-menthyl acetate, d,1-menthyl acetate, homomenthylacetate, menthyl lactate, 1-menthyl lactate, menthyl succinate,monomenthyl succinate, and combinations thereof.
 17. A chewing gumcomposition comprising the cooling composition of claim
 14. 18. Aconfectionery composition comprising the cooling composition of claim14.
 19. A cooling composition consisting essentially of: about 5% toabout 60% by weight menthyl glutarate; about 5% to about 50% by weightof at least one cooling agent selected from the group consisting ofN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof; and about 15% to about 85% by weight menthol,wherein said composition is liquid at 25° C.
 20. The cooling compositionof claim 19, wherein said menthyl glutarate is selected from the groupconsisting of monomenthyl monomenthyl 2-methylmaleatementhyl glutarate(FEMA 4006), monomenthyl glutarate ester, dimenthyl glutarate ester, anda menthyl half acid ester derivative.
 21. A chewing gum compositioncomprising the cooling composition of claim
 19. 22. A confectionerycomposition comprising the cooling composition of claim
 19. 23. Acooling composition consisting essentially of: about 5% to about 60% byweight of at least two menthyl esters; about 5% to about 50% by weightof at least one cooling agent selected from the group consisting ofN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof; and about 15% to about 85% by weight menthol,wherein said composition is liquid at 25° C.
 24. The cooling compositionof claim 23, wherein said at least two menthyl esters are selected fromthe group consisting of monomenthyl monomenthyl 2-methylmaleatementhylglutarate (FEMA 4006), monomenthyl glutarate ester, dimenthyl glutarateester, a menthyl half acid ester derivative, menthyl acetate, 1-menthylacetate, d,1-menthyl acetate, homomenthyl acetate, menthyl lactate,1-menthyl lactate, menthyl succinate, monomenthyl succinate, andcombinations thereof.
 25. A chewing gum composition comprising thecooling composition of claim
 23. 26. A confectionery compositioncomprising the cooling composition of claim
 23. 27. A coolingcomposition comprising: menthyl succinate; a second cooling agentselected from the group consisting of N-ethyl-p-menthane-3-carboxamide,trimethyl isopropyl butanamide and combinations thereof; and a thirdcooling agent selected from the group consisting of 1-isopulegol,p-menthane-3,8-diol and combinations thereof.
 28. The coolingcomposition of claim 27, wherein said menthyl succinate is selected fromthe group consisting of monomenthyl succinate, dimenthyl succinate andmonomenthyl α,α-dimethyl succinate.
 29. A chewing gum compositioncomprising the cooling composition of claim
 27. 30. A confectionerycomposition comprising the cooling composition of claim
 27. 31. A methodof preparing a cooling composition which is liquid at 25° C., comprisingthe steps of: (a) providing menthyl glutarate in a liquid form; and (b)adding at least one cooling agent selected from the group consisting ofN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof to the menthyl glutarate and dissolving orsuspending the at least one cooling agent therein to form the liquidcooling composition, wherein the menthyl glutarate is present in amountsof about 5% to about 60% by weight of the composition and the at leastone cooling agent selected from the group consisting ofN-ethyl-p-menthane-3-carboxamide, trimethyl isopropyl butanamide andcombinations thereof is present in amounts of about 5% to about 50% byweight of the composition.
 32. The method of claim 31, furthercomprising the step of adding menthol in amounts of about 15% to about85% by weight of the cooling composition.
 33. A method of preparing acooling composition which is liquid at 25° C., comprising the steps of:(a) combining menthyl glutarate and at least one cooling agent selectedfrom the group consisting of N-ethyl-p-menthane-3-carboxamide, trimethylisopropyl butanamide and combinations thereof; (b) heating the menthylglutarate and the at least one cooling agent to form a liquidcomposition; and (c) cooling the composition of the menthyl glutarateand the at least one cooling agent to less than 30° C. while maintainingthe composition in a liquid state to form the liquid coolingcomposition.